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United States Patent r 2,803,624 I METAL-CONTAINING POLYAZO DYESTUFFS Hans-Rudolf Byland, Riehen, near Basel, Switzerland,

assignor, by mesne assignments, to Saul & Co., Newark,

N. J., as nominee of Fidelity Union Trust Company, executive trustee under Sandoz Trust No Drawing. Application February 28, 1955, Serial No. 491,202

Claims priority, application Switzerland March 5, 1954 6 Claims. (Cl. 260-145) The present invention relates to metal-containing, especially copperand nickel-containing polyazo dyestuffs which, in the metal-free form, correspond to the formula wherein x stands for -OH, OCH3, OC2H5 or -COOH, R stands for hydrogen ora radical of the aliphatic, alicycli-c, araliphatic or aromatic series, R1 stands for a monoor binuclear radical of the benzene series, y stands for the radical of an hydroxynaphthalene compound and is linked to the respective -N=N group in ortho-position to the hydroxy group of said hydroxynaphthalene compound, radicals of the composition A being included, and wherein OH adjacent to R1 is located in ortho-position to the respective N=N- group.

The aforesaid metal-containing polyazo dyestuffs are obtained by treating the metal-free polyazo dyestufir's of Formula I with metal-yielding agents. Suitable metalyielding agents are for example copper compounds and HzN 0 28 "ice sulfonic acid, sulfonic acid amide and alkyl-sulfonyl groups, to assure the water-solubility of the metal-containing compounds. The nickel-containing dyestuffs are correspondingly prepared.

Metal-containing polyazo dyestuffs which are soluble in water, but the solubility of which does not exceed a certain limit, frequently possess particularly good affinity for cellulose fibers. On the other hand, this type of dyestulf, even if barely soluble in warm water, can also be readily employed for dyeing at temperatures above 100 C. under pressure.

Among the metal complex-forming groups x, the 0H, OCHs and COOH groups are the most important. Since dealkylating metallization such as is here involved will, in the case of a OCH2.COOH group, result in the splitting off of the entire CHzCOOH group, it is hardly practical to use polyazo dyestuffs which contain such groups.

The new metal-containing polyazo dyestulfs of the present invention are distinguished by their good tolerance to or compatibility with salt, and by the clear, deep navy blue shades of their dyeings on cotton and fibers of regenerated cellulose. The dyeings are dischargeable, of very good light fastness, and of good to very good fastness to washing and to water. Those dyeings are particularly fast which are aftertreated with polyalkylene-polyamine preparations which contain copper, e. g. in complex-bound form. In addition, the new dyestuffs reserve acetate silk and are also useful for printing and padding.

The following examples illustrate the invention by means of presently-preferred exemplary embodiments thereof. In such examples the parts are by weight, the percentages are by weight and the temperatures are in degrees centigrade.

Example 1 108.4 parts of the trisazo dyestuff which corresponds to the formula uCeHN- the metal complex compounds contain the requisite number of "solubilizing groups, such for example as carboxyl,

HzNOzS $0211 HOaS- 0H 11.05 5 cm H s 03H are suspended in 100 parts of pyridine, 15 parts of sodium carbonate and 50 parts of 25% aqueous ammonia in 2000 parts of water. The mixture is heated to whereby the dyestutf in part goes into solution. Thereupon, at 90 and in the course of a half hour, the solution of 76 parts of crystalline copper sulfate and 200 parts of 25 aqueous ammonia is added dropwise to the reaction mass. The mixture is boiled for 24 hours under reflux; in the course of this operation, the copper complex compound which is formed goes entirely into solu-' tion. The solution is then allowed towel and the coppercontaining trisazo dyestuif which corresponds to the formula IN=N (h-cii-N- SOsH SOaH 2,803,624: s 4 is salted out by the addition of 300 parts of sodium cellulose in navy blue shades of remarkable fastness chloride. The dyestuif is filtered off and dried. It is properties. a dark powder which dissolves with deep blue coloration Example 3 in water and dyes cotton and fibers of regenerated cellulose in navy blue shades of remarkable fastness 5 105.6 parts of the trisazo dyestufi which corresponds properties. to the formula zNOzB H506HN S0211 HO: 808E N N N==N H H H ExampleZ are suspended in 400 parts of molten sodium acetate which contains water of crystallization. 80 parts of crystalline copper sulfate are added to the molten mixture which is then heated under reflux for 24 hours, with 108.4 parts of trisazo dyestuff, used as starting material in Example 1, are dissolved together with 100 parts of pyridine, parts of sodium carbonate and '50 parts of 25 25% aqueous ammonia in 2000 parts of water. A solu- S The mixtlll'e is Then i with 2000 Parts tion of 79 parts of crystalline nickel sulfate (NiSO4.6H2O) of water, after whgch the preclnltated copper complex a d 400 parts of 25% aqueous ammonia r dd d t compound of the trisazo dyestufi 1s filtered off and dried.

the resultant solution in the course of a half hour; the The so-obtained copper-containing trisazo dyestulf correentire reaction mass is then boiled under reflux for 24 sponds to the formula HzNOzS N=N V ,1 I --Cu-IIT 501E H038 SOaH N\=N N=,N- 1 Cu-- --ci1 hours. Thereupon the solution is allowed to cool, the and possesses properties similar to those of the copper formed nickel complex compound of the trisazo dyestutf Complex compound described in EJ011111]?1e is salted out by the addition of 300 parts of sodium chlo E l 4 ride, and the precipitated product filtered off and dried. procedure according to Example 3 is followed The so-obtained nickel-containing trisazo dyestuif which except h h 0 parts f crystalline copper Sulfate are corresponds to the formula replaced by 79 parts of crystalline nickel sulfate. There ,I oN'iN son-1 H038 N\=N N=IN I --Ni$ d-N'i SOaH is a dark powder which dissolves with deep blue colorais thus obtained the corresponding nickel-containing tn'stion in water and dyes cotton and fibers of regenerated azo dyestufi of the formula which has properties similar to those of the nickel co'mplex compound described in Example 2.

The following table sets forth additional metal-containing polyazo dyestufls which can be prepared according to the processes set forth in the preceding examples 5 and which in the metal-free state correspond to the formula z. Column 5 indicates the metal contained in the metal complex compound, and column 6 sets forth the shades l I of the dyeings obtained on cellulose fibers with the metalx r (H) containing polyazo dyestuffs.

TABLE Monoazo Compound Corresponding to Moiety A Shade of Example No. 1 Second Azo Component Metal Dyeing on Cellulose ibcrs R Moiety {R OH Derived From- OCH; -CiHi 1 amino 2 hydroxy 5 methylsul- 1 hydroxynaphthalene 3,6 disul- Cu Navy bl fouylbenzene. ionic acid. -0CH; -CHs 1 amino 2 hydroxy 5 ethyisul- 1 acetylamino 8 hydroxynaphthaon Do,

fonylbenzene. lane-3,6-disulfouic acid. 0 CH3 -CaH 1 amino 2 hydroxybenzene 5 sul- 2 hydroxynaphthalene 3,6 disul- Cu D ionic acid amide. ionic acid. OC2H5 -C0H5 1 amino 2 hydroxybenzene 5 sui- 1 hy droxynaphthalene 3,6,8 --trisu1- on D ionic acid-phenylamide. ionic acid. 0 O l-I5 C5H5 1 amino 2 hydroxybenzene 5 sul- 2 phcnylamino 5 hydroxynaphtha- On D fonig acid (2 hydroxy) ethyliene-7,4-disu1fonic acid. am e. -OCH3 CcH4-SOaH 1 amino 2 -hydxoxybenzene 5 5111- 2 hydroxynaphthalene 4 sulfonic on D tonic acid methylamide. acid. -OCH; CoH4-SO9H 1 amino 2 hydroxybeuzene 5 sul- 1 acetylamino 8 hydroxy -naphtha- C D ionic acid morpholide. lene-esulfomc acid. OOH3 OaH4-SO H 1 amino 2 hydroxybcnzcnc 4 sul- 2 (4 carboxyi) phcnylamino 8 hy- Cu D ionic acid amide. droxynaphthalene-B-sulionic acid. 0OH -C0H4- CH; 1 amino 2 hydroxybenzene 5 5111- 1,8 dihydroxynaphthalene 3,6 disul- Cu D ionic acid amide. tonic acid. OCH; CaH1-C1 1 -famino 1% hydroxybenzcnc 5 sul- 1 hydroxyuaphthalene 4 sulfonic C D onic aci ac i OCH -C@H 1 amino 2 hydroxy 5 nitroben- 1 hydrogtynaphthalene 3,6 disul- (i D zene. ionic acid. 16 0 CH H 1 amino 2 hydroxy 5 chloroben- 1 hydro aphthalcne 3,8 disul- C D zene. ionic acid. 17 OCH C@H5 1 amino 2 hydroxybenzene 5 sul- ..d0 on D foni(c1 acid (4 methyl) phenylaml e. 18 -0CHa -CaH5 1 -amino 2- hydroxybenzene 5 -sul- 1 hydroxynaphthalene 3,6 di ul- Qu ionic acid methylamide. ionic acid. 19 OH -OaH -SO,H 1 amino 2-hydroxybenzeue 4 sul- 1 hydroxynaphthalene 4 suiionic o D ionic acid methylamide. acid. 20 --OOH -OH -SO H 1 amino 2 hydroxybenzene 5 sul- 1 (2 hydroxy 5 'sulfamido) phencu D ionic acid methylamide. ylazo 2 (4 sulfo) -phenylamino- 5 lgydroxynaphthalene 7 sulfonic ac 21 COOH -CoH4'SOaH -.--d0 Gu Do. 22 -COOH CeH -SO H 1 amino 2 hydroxy 5 methylsul- .do on D fonylbenzene. 23 -0CH CaH do 2 (4 cal-boxy) phenylamino 8 hyo D droxynaphthalene 6 sulfonic acid. 24 -O CH; CeH5 1 amino 2 hydroxybcnzcne 5 5111- 1 hydroxynaphthalene 3,6 disuio D fonig acid (3 methoxy) propyltonic acid. am e. 25 OCH C@H6 1 amino 2 hydroxybenzene 5 sul- .dc on D 011:3 acid (2-hydroxy) propylam e. 26 OH -C0H -S0 H 1 amino 2 -hydroxybenzene -4 sui- 1 [2 hydroxy 4 sulfo (2 hy- Ou D tonic acid (2 hydroxy) propyldroxy) propylamido] phcnylazoamide. 2 (4 sulfo) phenyiammo 5 hydroxynaphthaleue 7 sulfonic acid. C5H5 do 1 hydroxynaphthalene 3,6,8 trisui- 011 Do.

ionic acid. 28 i. -OCH -CH -SO2NH, 1 amino- 2 -hydroxybcnzene 5 sui- 1 [2 hydroxy 5 sulio (2 hycu D ionic acid (2' hydroxy) propyldroxy) propylamido] phenylazo amide. 2 (4 suifo) phenylamino 5 hydroxynaphthaleue 7 sulfonic acid. 29 OOH; CeH -SO H 1 amino 2 hydroxy 5 nitroben- 1 (2' hydroxy 5 su1iamido)- phen- N1 D zene. ylazo 2 (4 sulfo) phenylamino- 5 -igydroxynaphthalene 7 suifonio ac OCH1 -GQH4'SO3H 1 amino 2 hydroxy 4 nitroben- 1 (2 -hydroxy -4 -nitro) -pheny1azo- Cu Do. zene. 2- (4 sulfo) phenylamino 5 hydroxynaphthalene 7 sulfonic acid. -OCH@ -CnHu i-amino -2-hydr0xybenzene-5-su1- 1 hydroxynaphthaiene 3,6 disul- Cu Do.

tonic acid amide. ionic acid. -OCH3 CaH1a d0 011. D0.' OCH; CHz-CaH5 -----d0 Cu D0. -O CH; --CH:-C5H5 1 acetylamino 8 hydroxynaphtha- Ni Do.

, lene 3,6 disuifonic acid. OCH| -CaHu --do .-do Cu Do.

Formulae of representative dyestuffs of the preceding table are as follows:

The polyazo dyestuffs which serve as starting materials are prepared, for example, by coupling one mol of the tetrazo compound of a 4,4'-diamino-1,1'-diphenyl of the formula wherein x has the precedingly-indicated significance, with two mols of an azo compound of the formula (III) ynaphthalene compound coupling ortho-position to the hydroxy group.

Example36 100 parts of cotton which have been prewetted in hot water, are entered at 40 into a dyebath which contains a solution of 1.5 parts of the copper-containing polyazo dyestufl, prepared according to Example 1, and parts of Glaubers salt in 3000 parts of softened water. The bath is heated to 100 in the course of about 30 minutes, 20 additional parts of Glaubers salt being added portionwise, and the dyeing process is continued for minutes at 100 parts of urea and 45 parts of triethanolamine in '360 parts of water. 400 parts of gum tragacanth (6%),

100, at the end of which time 10 more parts of Glaubers Fibers of regenerated cellulose are dyed in the same' way.

Example 37 15 parts of the copper-containing polya'zo dyestufi' described in Example 1 are heated to boiling together with of a Foulard onto cotton fabric.

parts of sodium phosphate, 40 parts of an anion-active wetting agent and 10 parts of an anti-foaming agent are added to the solution, and the so-forrned printing paste is printed onto a fabric of viscose silk. The print is then dried, steamed for 45-60 minutes and rinsed. After a 15 minute after-treatment with one gram per liter of a copper salt-containing polyalkylene-polyamine preparation at 60, the print is again rinsed and dried.

Example 38 22.5 parts of the copper-containing trisazo dyestuif obtained according to Example 1 are dissolved in 1000 parts of boiling distilled water. The solution is allowed to cool and is then applied in the cooled state by means After expressing of the solution (relative to the weight of the cotton), a navy blue dyeing is obtained. In order to fix the soapplied dyestuff, the dyed cotton is subjected to a treatment in a steam bath or in a hot salt bath, for example a bath containing 20 grams of sodium chloride per liter. The dyed material is thereafter rinsed and dried.

What is claimed is:

1. A metal-containing polyazo dyestuff wherein the metal is selected from the class consisting of nickel and copper, and which, in the metal-free state, corresponds to the formula N =N R1- 0 H H 0 35- NH-- R t i no wherein x stands for a'member selected from the group consisting of --OH, OCHz, OC2H5 and COOl-I, R stands for a member selected from the group consisting of hydrogen, lower alkyl, cyclohexyl, benzyl and mononuclear carbocyclic aryl, R1 stands for a member selected from the group consisting of' mononuclear and binuclear radicals of the benzene series, y stands for the radical of an hydroxynaphthalene compound and is linked to the adjacent N=N group in orth0-position to the hydroxy group of said hydroxynaphthalene compound, and wherein OH adjacent to R1 is located in ortho-position to the adjacent N=N- group.

2. The copper complex compound which corresponds to the formula HzNOzS N: I -o 1N- -so311 H038- N=N- N=N- I -ou-c 0- o 1 (5 50m 3. The nickel complex compound which corresponds to the formula HRNO 2S O--Ni-N SOaH H088 Hzso N=N N=N l Ni-J) -Ni-- 03H 4. The copper complex compound which corresponds to the formula N=N 1 oi1 1 r- SOaH HOaS- SOaH N=N N=N II I Ou- -On 5. The copper complex compound which corresponds to the formula HaCHN 023 I I CuI| SOaH HO: SOaH N =N N=N Cu- Ou 6. The copper complex compound which corresponds to the formula HaCHNOzS BOINHI NI==N SOaH H0 N-Ou- References Cited in the file of this patent UNITED STATES PATENTS 2,638,468 Wehrli May 12, 1953 

1. A METAL-CONTAINING POLYAZO DYESTUFF WHEREIN THE METAL IS SELECTED FROM THE CLASS CONSISTING OF NICKEL AND COPPER, AND WHICH, IN THE METAL-FREE STATE, CORRESPONDS TO THE FORMULA 